CN1298556A - Active material of positive electrode for non-aqueous electrode secondary battery and method for preparing the same and non-aqueous electrode secondary battery using the same - Google Patents

Active material of positive electrode for non-aqueous electrode secondary battery and method for preparing the same and non-aqueous electrode secondary battery using the same Download PDF

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CN1298556A
CN1298556A CN99805392A CN99805392A CN1298556A CN 1298556 A CN1298556 A CN 1298556A CN 99805392 A CN99805392 A CN 99805392A CN 99805392 A CN99805392 A CN 99805392A CN 1298556 A CN1298556 A CN 1298556A
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positive electrode
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CN1206758C (en
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松本和顺
辻村富雄
武石和之
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Sumitomo Metal Mining Co Ltd
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Abstract

An active material of a positive electrode for a non-aqueous electrode secondary battery employing lithium cobaltate represented by the formula LiCoO2, which comprises a mixture of primary particles of small crystals having a Feret's diameter in a projection drawing by SEM observation in a range from 0.4 to 10 mu m and an average diameter of 5 mu m or less, and secondary particles formed by coagulation of the primary particles and having a diameter of 4 to 30 mu m, wherein the mole ratio of Co to Li is 0.97 to 1.03, at least a part of small crystals constituting the secondary particles are jointed by the junction through sintering, and the secondary particles are in the shape of a circle or an ellipse. And also are provided an active material of a positive electrode for a non-aqueous electrode secondary battery, wherein secondary particles account for 90% or more of the particles having a Feret's diameter of 9 mu m or more and particles having a Feret's diameter of 6 mu m or more constitute 70% or more by volume of the total mixture, which allows the improvement of discharge capacity, capability of keeping the level of discharge capacity, and high efficiency discharge capacity and a method for the production thereof, and a non-aqueous electrode secondary battery manufactured using the active material of a positive electrode.

Description

Be used for the positive electrode active materials and preparation method thereof of rechargeable nonaqueous electrolytic battery and the rechargeable nonaqueous electrolytic battery that uses this positive electrode active materials
The present invention relates to be used for the positive electrode active materials of rechargeable nonaqueous electrolytic battery, wherein lithium metal, lithium alloy etc. are used for negative pole, the present invention especially be involved in the positive electrode active materials of rechargeable nonaqueous electrolytic battery, particularly rechargeable nonaqueous electrolytic battery discharge capacity, efficient discharge capacity and battery discharge capacity conservation rate, prepare this positive electrode active materials and use the method for the rechargeable nonaqueous electrolytic battery of described positive electrode active materials to be improved.
Along with for example diffusion propagation of mobile phone, notebook personal computer or the like of portable set, the strong in recent years secondary cell of wishing to develop high-energy-density, small size, light weight and high power capacity.As for these batteries, there is wherein lithium, lithium alloy or carbon lithium rechargeable battery as negative pole, be devoted to finish the research and development of this battery.
Lithium-cobalt double oxide (LiCoO wherein 2) provide the high voltage of 4V level as the lithium rechargeable battery of positive electrode active materials, therefore, wish that battery has high-energy-density, and can drop into practicality.
Nearest more high power capacity and high power requirements more need be taken measures, and improve the packed density of positive electrode active materials or the quantity of the carbon that the reduction conductive materials for example mixes with positive electrode active materials, and this improves the quantity of positive electrode active materials basically.
Usually, LiCoO 2Be prepared as follows and carry out: with the lithium salts of some for example lithium carbonate and cobalt compound for example cobalt carbonate mix, calcination under 600 ℃-1100 ℃ temperature (the open No.304664/1989 of Japan Patent), or lithium carbonate and the cobaltosic oxide of the average grain diameter 2-25 μ m of some mixed, and calcination under 800 ℃-900 ℃ temperature (the open No.283144/1997 of Japan Patent).
Yet, traditional LiCoO 2Shortcoming is to improve the degeneration of the quantity decline guiding discharge capacity of packed density or conductive materials, and depends on discharge current density.
It is considered herein that this reason is as follows.Be LiCoO 2Have hexagonal lattice, therefore, form the lath body in right corner to the crystal growth on the direction of C axle in synthesizing.In addition, crystal is inhomogeneous dimensionally, therefore, mixes etc. to produce many defectives with conductive materials, is difficult to improve packed density.And, reduce the quantity of conductive materials and make the reason of discharge capacity or efficient discharge degradation in capacity think as follows.In the crystal that forms according to conventional method, carry out sintering under the high temperature sintering, this needs high-energy with levigate product in electrode preparation.The particle of the meticulous pulverizing of levigate generation, therefore increasing specific surface area, for conductance is provided, needs to add for example carbon of a large amount of conductive materials.
And when pulverizing active material in order to improve the efficient discharge performance more subtly so that high power flows, filling characteristic greatly reduces or comes off from collector body.
The objective of the invention is to solve the problem of above-mentioned positive electrode active materials, and be provided for the positive electrode active materials of rechargeable nonaqueous electrolytic battery, the conservation rate of the discharge capacity of rechargeable nonaqueous electrolytic battery, efficient discharge capacity and discharge capacity, prepare this positive electrode active materials and use the method for rechargeable nonaqueous electrolytic battery of positive electrode active materials good.
For addressing the above problem, the inventor further is devoted to study the former particle size and the shape of positive electrode active materials and assembles former particle and the size and dimension of the second particle that forms, find that these factors of control can obtain having the positive electrode active materials of high power capacity and good efficient discharge capacity, therefore finish the present invention.
Be that the first embodiment of the present invention is characterised in that the positive electrode active materials that is used for rechargeable nonaqueous electrolytic battery, wherein be used to use molecular formula LiCoO 2In the positive electrode active materials of the rechargeable nonaqueous electrolytic battery of the cobalt acid lithium of expression, above-mentioned cobalt acid lithium is assembled the scope that forms by the former particle of small crystals and granule and is constituted at the second particle of 4-30 μ m, the Feret diameter range that SEM observes the small crystals in the perspective view is 0.4-10 μ m, its average grain diameter is 5 μ m or littler, in addition, the mol ratio of Co and Li is 0.97 or bigger and 1.03 or littler.In addition, preferably constitute mutually combining by sintering to the small part small crystals of above-mentioned second particle, and above-mentioned second particle is spherical or oval spherical.
And, the first embodiment of the present invention is characterised in that the positive electrode active materials that is used for rechargeable nonaqueous electrolytic battery, wherein second particle account for SEM observe Feret diameter in the perspective view be 9 μ m or larger particle 90% or more, and SEM observe Feret diameter in the perspective view be the volume ratio of 6 μ m or larger particle account for total mixture 70% or bigger.
The second embodiment of the present invention is characterised in that preparation is used for the method for the positive electrode active materials of rechargeable nonaqueous electrolytic battery, wherein is used to use molecular formula LiCoO in preparation 2In the method for the positive electrode active materials of the rechargeable nonaqueous electrolytic battery of the cobalt acid lithium of expression, above-mentioned cobalt acid lithium is assembled the scope that forms by the former particle of small crystals and many above-mentioned granules and is constituted at the second particle of 4-30 μ m, the Feret diameter range that SEM observes the small crystals in the perspective view is 0.4-10 μ m, its average grain diameter is 5 μ m or littler, in addition, the mol ratio of Co and Li is 0.97 or bigger and 1.03 or littler, cobalt acid lithium is prepared as follows: lithium salts and cobalt source are mixed, wherein hydroxy cobalt oxide (CoOOH) is used as raw material and comprises the second particle of scope at 4-30 μ m, second particle forms by the former particle of assembling many 0.2-0.8 μ m, then, this mixture is heat-treated.In addition, the second particle of preferred above-mentioned positive electrode active materials is spherical or oval spherical, constitutes mutually combining by sintering to the small part small crystals of above-mentioned second particle.
The second particle of above-mentioned hydroxy cobalt oxide is spherical or oval spherical, account for SEM observe Feret diameter in the perspective view be 9 μ m or larger particle 90% or more, and particle diameter to be the volume ratio of 6 μ m or larger particle account for total mixture 70% or bigger.In oxidizing atmosphere, carry out said mixture under 800 ℃-1000 ℃ heat treatment 4-12 hour.Preferred cobaltosic oxide that obtains by 350 ℃ of-800 ℃ of following heat treatment oxyhydroxides in oxidizing atmosphere or the cobaltosic oxide that comprises the second particle of scope 4-30 μ m of using serves as the cobalt source, and to observe Feret diameter range in the perspective view be that the many former particle of 0.05-0.8 μ m forms by assembling SEM.
In addition, the second embodiment of the present invention is characterised in that preparation is used for the method for the positive electrode active materials of rechargeable nonaqueous electrolytic battery, and wherein the second particle of above-mentioned cobaltosic oxide is spherical or oval spherical.
The third embodiment of the present invention is characterised in that rechargeable nonaqueous electrolytic battery contains the positive electrode active materials relevant with first embodiment as composition.
Fig. 1 is the grain structure figure that is used for the ball shaped hydroxy cobalt oxide of example 1 by the expression of scanning electron microscopy;
Fig. 2 is the grain structure figure of resulting spherical cobalt acid lithium in the expression example 2 by scanning electron microscopy;
Fig. 3 is the chamfer map of the 2032 type coin batteries that lack of part, wherein uses the resulting positive electrode active materials of the present invention;
Fig. 4 is the grain structure figure that is used for the spherical cobaltic-cobaltous oxide of example 5 by the expression of scanning electron microscopy.
At the positive electrode active materials that is used for the rechargeable nonaqueous electrolytic battery relevant with the present invention, can improve the contact area of electrolyte and positive electrode active materials, utilizing SEM (SEM) to observe Feret diameter range in the perspective view is that 0.4-10 μ m and average grain diameter 5 μ m or less small crystals are as molecular formula LiCoO2The former particle of the cobalt acid lithium of expression obtains the correlation of good discharge current density.
Term used herein " the Feret diameter in the perspective view " means maximum length in the perspective view (especially in oval spherical measurement, the length on the length direction). Arrowhead to the reason of scope 0.4-10 μ m be size less than the decline of 0.4 μ m guiding discharge capacity and efficient discharge capacity, and on the other hand, the conservation rate that surpasses 10 μ m guiding discharge capacity descends. And the restriction average grain diameter is to surpass 5 μ m to cause for the first time decline of the conservation rate of discharge capacity and capacity to 5 μ m or less reason, therefore, is necessary for 5 μ m or less. Yet, be difficult to prepare Feret diameter range 0.4-10 μ m and average grain diameter 0.5 μ m or less small crystals, therefore, bottom line is 0.5 μ m.
Although the former particle self of above-mentioned small crystals is fine granular, at least part of former particle mutually combines by sintering, form the spherical or oval spherical second particle of average particle size range 4-30 μ m, this and above-mentioned former particle form the positive electrode active materials that comprises mixture. This causes the improvement of conductance, simultaneously, the former particle of small crystals is mixed the space that produces in the former particles filled second particle of available small crystals with second particle, improves packed density. Can greatly improve the filling characteristic of the positive electrode active materials of electrode, also can prevent from coming off the improvement of the raising of this guiding discharge capacity and the conservation rate of discharge capacity from collector body.
To be size to the reason of 4-30 μ m cause the decline of efficient discharge capacity less than 4 μ m to the particle diameter of restriction second particle, and on the other hand, surpasses 30 μ m and cause discharge capacity and the decline of the conservation rate of the capacity first time. By molecular formula LiCoO2Co in the cobalt acid lithium of expression and the mol ratio of Li must be 0.97 or larger and 1.03 or less. Reason is mol ratio less than 0.97 or surpasses 1.03 and cause the conservation rate of for the first time discharge capacity, capacity and descend with the correlation of discharge current density.
At the positive electrode active materials that is used for rechargeable nonaqueous electrolytic battery, preferred second particle account for SEM observe Feret diameter in the perspective view be 9 μ m or larger particle 90% or more, and described Feret particle diameter to be the volume ratio of 9 μ m or larger particle account for total mixture 70% or larger. Reason be when the Feret particle diameter in the perspective view be that the second particle ratio of 9 μ m or larger particle is less than 90% the time, recharge and discharge produce the fine crushing particle from large former particle, disconnect from collector body and to electrically contact or come off, this degenerates the conservation rate of capacity. And, when the Feret particle diameter in the perspective view be 6 μ m or larger particle volume ratio less than mixture 70% the time, improve add conductive materials for example the necessary amount of acetylene black to improve conductance, the decline of guiding discharge capacity or efficient discharge capacity. When improving conductance and improve the quantity of conductive materials, reduce the quantity in order to the positive electrode active materials of filling battery, cause the decline of the capacitance of battery.
Then, description is for the preparation of the method for the positive electrode active materials of rechargeable nonaqueous electrolytic battery. Have mentioned component by molecular formula LiCoO2The cobalt acid lithium of expression is prepared as follows: with for example lithium carbonate and the mixing of cobalt source of lithium salts, wherein hydroxy cobalt oxide (CoOOH) comprises the spherical or oval spherical second particle of scope 4-30 μ m, and form by the former particle of assembling as raw-material many 0.2-0.8 μ m, then mixture is heat-treated.
Hydroxy cobalt oxide is assembled in restricted passage and the second particle that forms is the sour lithium of cobalt that can not obtain having the second particle of desirable size outside scope to the reason of scope 4-30 μ m.
Preferably in oxidizing atmosphere, carry out said mixture under 800 ℃-1000 ℃ heat treatment 4-12 hour. The reason that is limited in 800 ℃ of-1000 ℃ of lower heat treatment 4-12 hours condition is less than 800 ℃ or less than 4 hours heat treatment or surpass 1000 ℃ or surpass 12 hours heat treatment and be difficult to obtain fully for the first time conservation rate and the efficient discharge capacity of discharge capacity, discharge capacity.
And, preferred cobaltosic oxide or the cobaltosic oxide that obtains by 350 ℃ of-800 ℃ of lower heat treatment oxyhydroxides in oxidizing atmosphere or the cobaltosic oxide that comprises the second particle of scope 4-30 μ m of using serves as the cobalt source, is that the many former particle of 0.05-0.8 μ m forms by assembling Feret particle size range in the perspective view. The second particle shape of above-mentioned cobaltosic oxide is restricted to sphere or oval spherical.
The restriction second particle is the compacted density (tap density) that can not provide enough for spherical or oval spherical reason, and because the uncertain shape except this shape also makes the efficient discharge degradation in capacity.
Except that lithium carbonate, lithium hydroxide, lithium nitrate etc. can be used as above-mentioned lithium salts.
Example
Example 1
Accurately the spherical or oval sphere of weighing formation scope 4-30 μ m is the hydroxy cobalt oxide (CoOOH) and the lithium carbonate (Li of the second particle of basic configuration 2CO 3), form second particle by the former particle of assembling many 0.2-0.8 μ m, shown in the SEM photograph of Fig. 1, thereby the mol ratio of Li and Co has composition as shown in table 1 below, mix and grating with the stainless steel mixing breaker that is equipped with stirring vane and blender, add polyvinyl alcohol resin (PVA) aqueous solution simultaneously, make the quantity of PVA be about 1.4 parts of weight, and powder is 100 parts of weight.
Then, be crushed to the said mixture 5 hours of 3-5mm, calcination under the various conditions shown in the table 1 afterwards 120 ℃ of following dryings.
Utilize inductively coupled plasma atomic spectrograph (ICP) to analyze resulting cobalt acid lithium composition, change the charging composition shown in the table 1 hardly.Utilize the K alpha ray of Cu to determine formed phase by powder x-ray diffraction, detect and have only micro-Li 2CO 3And Co 3O 4Phase, as the LiCoO that removes JCPDS card No.16-427 2Outside phase.
Control the size of resulting cobalt acid lithium through the sieve of 32 μ m openings, carry out SEM and observe.The result, be defined as Feret particle size range 0.4-10 μ m in the perspective view and average grain diameter 5 μ m or littler granule and have sphere or the mixture of oval spherical second particle, second particle is assembled by many above-mentioned granules and is formed, and scope is 4-30 μ m, as can be seen from Figure 2.
Then, observing the former particle of part that confirms the formation second particle by * 15000 SEM that amplify mutually combines by sintering.And the ratio of about 9 μ m of Feret particle diameter in * 600 SEM photographs that amplify in the perspective view of inspection said mixture or bigger particle, second particle and former particle finds that all second particles account for 98% or bigger.
And, utilize little footpath (microtrack) particle size distribution measuring instrument to detect the particle size distribution of said mixture, find that the Feret particle diameter 6 μ m in each perspective view or the cumulative volume percentage of bigger particle are 90% or bigger.
Control the cobalt acid lithium of the some (50 gram) of particle diameter as mentioned above and place measurement at volume 1OOcm 3The measurement tube in, measure tube and highly drop on the sheet rubber of hardness 60-80 from 50cm, repeat 200 times so that compacting.After finishing compacting, read the sample volume of measuring in the tube, calculate compacted density, shown in the table 1.
And, utilize resulting cobalt acid lithium as active material assembled battery, measure charging and discharge capacity.Positive electrode active materials, acetylene black and the polyflon (PTFE) that mix above-mentioned cobalt acid lithium with weight ratio at 80: 15: 5, preparation depolarising mixture, weigh the above-mentioned depolarising mixture of 50mg, under 200Mpa pressure, be molded into the disk of 10mm φ diameter.
Dry resulting disk spends the night under 120 ℃ in vacuum desiccator, and preparation is anodal.Use positive plate 5 and be used for the diameter phi 16mm of negative pole and the Li sheet metal 2 of thickness 1mm, as shown in Figure 3.Use contains the ethylene carbonate (EC) and 1 of equal number, and the 1mol LiPF of salt is supported in 2-dimethoxy-ethane (DME) and conduct 6Serve as electrolyte.The polyethylene porous membrane of thickness 25 μ m seals as dividing plate 3 and with packing ring 4.Dew point is controlled at assembling 2032 type Coin-shaped batteries in-80 ℃ the glove box under Ar atmosphere.
Among Fig. 3, the 1st, negative electrode casing, the 6th, anode cover, electrolyte are present in the inside battery slit, although electrolyte does not illustrate in the drawings.
Prepared Coin-shaped battery was placed about 10 hours after assembling.Stablizing open circuit voltage (OCV) afterwards, with density of charging current 1.0mA/cm 2To battery charge,, placed afterwards 2 hours, with discharge current density 1.0mA/cm until off voltage 4.3V 2Finish discharge test, until 3.0V.The result of discharge capacity is as shown in table 1.
Recharge and discharge test under aforesaid condition after repeated experiments 100 times, calculate the conservation rate of discharge capacity according to following equation 1.
Equation 1
The conservation rate of discharge capacity (%)=100 time discharge capacity/first time discharge capacity * 100
Table 1
The experiment number Li/Co (mol ratio) Calcination temperature (℃) hour Atmosphere Compacted density g/cm 3 Very first time discharge capacity mAh/g The conservation rate of capacity
????1 ?0.97 ?1000/4 Air ??2.65 ????151 ????80
????2 ?1.00 ?900/8 Air ??2.63 ????150 ????84
????3 ?1.03 ?800/12 Air ??2.70 ????147 ????81
????4 ?1.01 ?900/6 Air ??2.71 ????150 ????82
????5 ?1.00 ?900/8 Air ??2.69 ????152 ????83
????6 ?1.02 ?850/8 Oxygen ??2.68 ????145 ????80
????7 ?0.99 ?900/10 Air ??2.70 ????144 ????81
????8 ?0.98 ?950/8 Air ??2.65 ????143 ????81
????9 ?1.00 ?950/6 Air ??2.70 ????149 ????84
????10 ?1.00 ?900/8 Oxygen ??2.69 ????152 ????93
Example 2
Under the calcination condition shown in the table 2, utilize the used hydroxy cobalt oxide of example 1 and the composition of lithium carbonate to obtain cobalt acid lithium in the mode that is similar to example 1.Assess resulting cobalt acid lithium in the mode that is similar to example 1.Its composition changes the charging composition shown in the table 2 hardly, removes the Li that only detects trace 2CO 3And Co 3O 4Phase does not confirm that formed is LiCoO mutually 2Outside phase.
Determine that cobalt acid lithium is Feret particle size range 0.4-10 μ m in the perspective view and average grain diameter 5 μ m or the littler granule and the mixture of spherical or oval spherical second particle, second particle is assembled by many above-mentioned granules and is formed, and scope is 4-30 μ m.And, confirm that the former particle of part that constitutes second particle mutually combines by sintering.Also confirm in said mixture, the volume ratio of Feret particle size range 6 μ m in the perspective view or bigger particle be mixture 90% or more, in addition, second particle account for Feret particle size range 9 μ m in the perspective view or bigger particle 98% or more.
Be similar to example 1, utilize resultant cobalt acid lithium to serve as positive electrode active materials, assemble battery shown in Figure 3.According to discharge current density pertinence, the efficient discharge capacity of the resulting Coin-shaped battery of following assessment.
That is, above-mentioned Coin-shaped battery was placed about 10 hours after assembling.Stablizing open circuit voltage (OCV) afterwards, with density of charging current 1.0mA/cm 2To battery charge,, placed afterwards 2 hours, with discharge current density 1.0mA/cm until off voltage 4.3V 2Finish discharge test,, find discharge capacity (1) until off voltage 3.0V.Outside, after finishing discharge test, deposited then 2 hours, once more with density of charging current 1.0mA/cm 2To battery charge,, placed afterwards 2 hours, with discharge current density 8.0mA/cm until off voltage 4.3V 2Finish discharge test,, find discharge capacity (8) until off voltage 3.0V.According to the pertinence of following equation 2 calculating with discharge current density.The result is as shown in table 2.
Equation 2
Correlation=discharge capacity (8)/discharge capacity (1) * 100 with discharge current density
Table 2
The experiment number Li/Co (mol ratio) Calcination temperature (℃)/hour Atmosphere Correlation (%) with discharge current density
????11 ????0.97 ????980/5 Air ????62
????12 ????1.00 ????900/8 Air ????68
????13 ????1.03 ????850/12 Air ????61
????14 ????1.00 ????900/6 Oxygen ????67
????15 ????1.00 ????950/8 Air ????70
Example 3
The various samples that have shown in the table 3 of the resulting cobalt acid of example 1 lithium number utilize centrifugal grinder that sample segment is milled down to 6 μ m or littler.With right quantity resulting levigate powder is mixed with raw sample, thereby the volume factor (volume ratio) of 6 μ m in the mixed-powder or bigger particle is as shown in table 3, therefore obtains mixed-powder.Be similar to the compacted density that example 1 detects resulting mixed-powder, as shown in table 3.
Utilize above-mentioned mixed-powder to serve as active material in the mode that is similar to example 1, prepare Coin-shaped battery shown in Figure 3.The conservation rate of discharge capacity and 100 discharge capacities is represented in table 3 for the first time.
Table 3
The experiment number In the example 1 number The volume factor (%) of 6 μ m or bigger particle Compacted density g/cm 3 Discharge capacity mAh/Gg for the first time The conservation rate of capacity (%)
????16 ????1 ????90 ????2.74 ????151 ????80
????17 ????2 ????80 ????2.80 ????150 ????84
????18 ????3 ????90 ????2.75 ????147 ????81
????19 ????5 ????70 ????2.85 ????152 ????83
????20 ????8 ????85 ????2.80 ????149 ????84
????21 ????10 ????95 ????2.76 ????152 ????83
Example 4
The various samples that have shown in the table 4 of the resulting cobalt acid of example 1 lithium number carried out calcination again 24 hours to sample segment under 1000 ℃ in electric furnace, air is passed through.In the product of calcination again, carry out the growth of former particle, obtain particle diameter 9 μ m or bigger many particles.Utilize centrifugal grinder with these samples levigate after, with the sieve collect 9 μ m or bigger and 30 μ m or littler particle, obtain thick former particle.Obtain above-mentioned thick former particle, thereby the volume factor of second particle is as shown in table 4, about 9 μ m or bigger particle in the mixed-powder mix with raw sample with right quantity, obtain mixed-powder.Be similar to the compacted density that example 1 detects resulting mixed-powder, as shown in table 4.
Utilize above-mentioned mixed-powder to serve as active material in the mode that is similar to example 1, prepare Coin-shaped battery shown in Figure 3.The conservation rate of discharge capacity and 100 discharge capacities is represented in table 4 for the first time.
Table 4
The experiment number In the example 1 number The volume factor of second particle (%) Compacted density g/cm 3 Discharge capacity mAh/g for the first time The conservation rate of capacity (%)
????22 ????2 ????95 ????2.62 ????149 ????83
????23 ????3 ????97 ????2.68 ????146 ????82
????24 ????4 ????94 ????2.68 ????148 ????81
????25 ????10 ????90 ????2.65 ????147 ????80
Example 5
Hydroxy cobalt oxide (CoOOH) calcination under the conditions shown in Table 5 that example 1 is used obtains cobaltosic oxide (Co 3O 4).All resulting Co 3O 4Be the spherical or oval spherical second particle of the scope 4-30 μ m that serves as the particle principal mode, to observe Feret particle diameter in the perspective view be that the many former particle of 0.2-0.8 μ m forms by assembling SEM, as shown in Figure 4.
To be similar to the mode of example 1, utilize resulting Co 3O 4Serve as composition shown in cobalt source and the table 5 and condition, obtain cobalt acid lithium.Composition changes the charging composition shown in the table 5 hardly.Remove the Li that only detects trace 2CO 3And Co 3O 4Phase, not observing formed is to remove LiCoO mutually 2Outside phase.
Determine that cobalt acid lithium is Feret particle size range 0.4-10 μ m in the perspective view and average grain diameter 5 μ m or the littler granule and the mixture of spherical or oval spherical second particle, second particle forms by many above-mentioned granules gatherings, and scope is between 4-30 μ m.
And, confirm that in the former particle that constitutes second particle, part mutually combines by sintering.In said mixture, the volume ratio of Feret particle size range 6 μ m in the perspective view or bigger particle be defined as mixture 90% or more.In addition, determine second particle account for Feret particle size range 9 μ m in the perspective view or bigger particle 98% or more.
Then,, detect compacted density to be similar to the mode of example 1, as shown in table 5.
To be similar to the mode of example 1, utilize resulting lithium cobalt double oxide to serve as active material and prepare Coin-shaped battery, detect discharge capacity.The result is as shown in table 5.
Table 5
The experiment number The CoOOH calcination temperature (℃) Li/Co (mol ratio) Calcination temperature (℃)/hour Atmosphere Compacted density g/cm 3 Discharge capacity mAh/g for the first time The retention rate of capacity (%)
????26 ????350 ????1.00 ????900/4 Air ????2.64 ????145 ????80
????27 ????500 ????1.00 ????900/8 Air ????2.68 ????150 ????81
????28 ????800 ????1.03 ????900/8 Air ????2.66 ????146 ????80
????29 ????700 ????0.97 ????900/6 Air ????2.65 ????150 ????82
????30 ????400 ????1.00 ????900/8 Air ????2.70 ????152 ????84
????31 ????500 ????1.00 ????850/12 Oxygen ????2.67 ????147 ????80
????32 ????450 ????1.00 ????950/6 Air ????2.68 ????151 ????83
????33 ????600 ????1.00 ????950/6 Oxygen ????2.70 ????151 ????82
????34 ????750 ????1.00 ????1000/4 Air ????2.66 ????152 ????80
????35 ????450 ????1.00 ????950/6 Oxygen ????2.69 ????150 ????94
Example 6
The various samples that have shown in the table 6 of the resulting cobalts acid of example 5 lithiums number utilize centrifugal grinder that sample segment is milled down to 6 μ m or littler.With right quantity resulting levigate powder is mixed with raw sample, thereby the volume factor (volume ratio) of 6 μ m in the mixed-powder or bigger particle is as shown in table 6.Be similar to the compacted density that example 1 detects resulting mixed-powder, as shown in table 6.
Utilize above-mentioned mixed-powder to serve as active material in the mode that is similar to example 1, prepare Coin-shaped battery shown in Figure 3.The conservation rate of discharge capacity and 100 discharge capacities is represented in table 6 for the first time.
Table 6
The experiment number In the example 5 number The volume factor (%) of 6 μ m or bigger particle Compacted density g/cm 3 Discharge capacity mAh/g for the first time The conservation rate of capacity (%)
????36 ????26 ????70 ????2.85 ????153 ????84
????37 ????27 ????80 ????2.83 ????152 ????81
????38 ????28 ????90 ????2.75 ????149 ????80
????39 ????32 ????70 ????2.88 ????154 ????82
????40 ????33 ????85 ????2.83 ????152 ????93
????41 ????35 ????95 ????2.72 ????151 ????84
Example 7
The various samples that have shown in the table 7 of the resulting cobalts acid of example 5 lithiums number carried out calcination again 24 hours to sample segment under 1000 ℃ in electric furnace, air is passed through.In the product of calcination again, carry out the growth of former particle, comprise particle diameter 9 μ m or bigger many particles.Utilize centrifugal grinder with these samples levigate after, with the sieve collect 9 μ m or bigger and 30 μ m or littler particle, obtain thick former particle.
Obtain above-mentioned coarse granule from above-mentioned thick former particle, thereby the volume factor of second particle is as shown in table 7, about 9 μ m or bigger particle in the mixed-powder is mixed with raw sample, obtain mixed-powder with right quantity.
Be similar to the compacted density that example 1 detects resulting mixed-powder, as shown in table 7.
Utilize above-mentioned mixed-powder to serve as active material in the mode that is similar to example 1, prepare Coin-shaped battery shown in Figure 3.The conservation rate of discharge capacity and 100 discharge capacities is represented in table 7 for the first time.
Table 7
The experiment number In the example 1 number The volume factor of second particle (%) Compacted density g/cm 3 Discharge capacity mAh/g for the first time The conservation rate of capacity (%)
????42 ????27 ????90 ????2.59 ????149 ????80
????43 ????28 ????95 ????2.63 ????143 ????80
????44 ????30 ????90 ????2.60 ????149 ????81
????45 ????35 ????92 ????2.64 ????148 ????82
Comparative example 1
Except that composition and calcination condition are as shown in table 8, be similar to example 1 and handle hydroxy cobalt oxide and the lithium carbonate that is used for example 1, therefore obtain cobalt acid lithium.
Utilize resulting cobalt acid lithium to serve as positive electrode active materials, prepare Coin-shaped battery, and according to the method for measurement of example 1 and 2, detect the correlation of conservation rate and the discharge capacity and the discharge current density of discharge capacity, 100 discharge capacities respectively, expression in table 8.
Table 8
The experiment number The Li/Co mol ratio Calcination temperature (℃/hour) Atmosphere Discharge capacity mAh/g for the first time The conservation rate of capacity (%) Correlation (%) with discharge current density
????46 ????0.95 ????950/4 Air ????140 ????75 ????61
????47 ????1.00 ????950/2 Air ????138 ????65 ????62
????48 ????1.05 ????850/12 Air ????147 ????70 ????58
????49 ????1.00 ????750/6 Air ????135 ????71 ????53
????50 ????1.00 ????1100/8 Air ????133 ????63 ????50
Comparative example 2
Accurately weighing is used for the hydroxy cobalt oxide and the lithium carbonate of example 1, thereby Co and Li become 1: 1, and being similar to the mode of example 1, and 900 ℃ of following calcinations are 8 hours in air, prepare the sour lithium of cobalt.By the levigate resulting part lithium cobalt of ball mill, thereby all particles become 6 μ m or littler.Then, thoroughly mix above-mentioned levigate cobalt acid lithium powder and not levigate powder, make weight ratio become 40: 60.The not enough 2.0g/cm of the compacted density of above-mentioned mixed-powder 3Prepare Coin-shaped battery shown in Figure 3 in the mode that is similar to example 1, the conservation rate of the detection discharge capacity first time and 100 discharge capacities.The conservation rate of capacity is 90%, and discharge capacity is low to moderate 135mAh/g for the first time.
Comparative example 3
Accurately weighing is used for the hydroxy cobalt oxide and the lithium carbonate of example 1, thereby Co and Li become 1: 1, and being similar to the mode of example 1, and 900 ℃ of following calcinations are 8 hours in air, prepare the sour lithium (I) of cobalt.The volume ratio of the second particle in the resulting cobalt acid lithium is 98%.In addition, at the cobaltosic oxide of the former particle that only comprises average grain diameter and lithium carbonate with 5 μ m by accurately weighing, thereby after Co and Li became 1: 1, being similar to the mode of example 1,900 ℃ of following calcinations were 8 hours in air, prepare the sour lithium (II) of cobalt.
In resulting cobalt acid lithium, carry out sintering, form second particle, therefore, levigate second particle is until the former particle of collecting 9-20 μ m with sieve.
Thoroughly mix resulting former particle and above-mentioned cobalt acid lithium at 10: 90 with volume ratio.
To be similar to the mode of example 1, utilize resulting mixture to prepare Coin-shaped battery shown in Figure 3, the conservation rate of the detection discharge capacity first time and 100 discharge capacities.Discharge capacity is 145mAh/g for the first time, and the conservation rate of discharge capacity drops to 73%.
Comparative example 4
Accurately weighing contains hydroxy cobalt oxide and the lithium carbonate as the former particle of key component particle grain size 0.2-0.8 μ m, thereby Co and Li become 1: 1, and being similar to the mode of example 1, and 900 ℃ of following calcinations are 8 hours in air, prepare the sour lithium of cobalt.
In resulting cobalt acid lithium, distinguish the former particle of sintering, form the second particle of uncertain shape and 0.4-10 μ m.Compacted density is low to moderate 1.8g/cm 3
Comparative example 5
Accurately cobaltosic oxide and the lithium carbonate of weighing average grain diameter 5 μ m, thus Co and Li become 1: 1, and and being similar to the mode of example 1,900 ℃ of following calcinations are 8 hours in air, prepare the sour lithium of cobalt.
Owing to the resulting cobalt acid of strong sintering lithium, form hard particles, levigate with centrifugal grinder, control the resulting granules size with the sieve of 32 μ m then.
The product of resulting size Control is former particle and the mixed-powder with second particle of uncertain shape, and particle size distribution is 0.2-32 μ m.The volume ratio of 6 μ m or bigger particle is 56%, and compacted density is low to moderate 2.1g/cm 3To be similar to the mode of example 1 and example 2, prepare Coin-shaped battery shown in Figure 3.The conservation rate of discharge capacity and 100 discharge capacities is respectively 138mAh/g and 84% for the first time, and the correlation of discharge capacity and discharge current density is low to moderate 54%.
Comparative example 6
Accurately cobaltosic oxide and the lithium carbonate of weighing average grain diameter 5 μ m, thus Co and Li become 1: 1, and and being similar to the mode of example 1,900 ℃ of following calcinations are 8 hours in air, prepare the sour lithium of cobalt.
Because the resulting cobalt acid of strong sintering lithium forms hard particles, and is levigate with centrifugal grinder, is milled down to 10 μ m or littler former particle by ball mill then.The PVA of a weight and the water of right quantity are joined in the resulting powder, stir, form slurry.
Utilize the have an appointment jet drier of multiple-blade type dish of 12cm diameter of equipment, grating slurry under the condition of 240 ℃ of rotating speed 1000rpm and hot air inlet temperature utilizes the sieve of 32 μ m to control resulting crystallite dimension.
The powder of resulting size Control is placed in the porcelain container, with 150 ℃/hour speed elevated temperature, until to 600 ℃, and makes air pass through electric furnace, keeps 2 hours, and PVA thoroughly volatilizees.
To be similar to the mode of example 1, to utilize resulting cobalt acid lithium grain to serve as positive electrode active materials and prepare Coin-shaped battery shown in Figure 3.The conservation rate of discharge capacity and 100 discharge capacities is respectively 136mAh/g and 78% for the first time, does not reach satisfied value fully.
Comparative example 7
Accurately weighing is used for the cobalt hydroxide (Co (OH) of conventional method 2) and lithium carbonate (Li2CO 3), cobalt hydroxide (Co (OH) in the conventional method wherein 2) spherical or oval spherical second particle scope be 4-30 μ m and form by the many former particle of assembling 0.2-0.8 μ m, as main particle form, thereby Co and Li become 1: 1, and to be similar to the mode of example 1,900 ℃ of following calcinations are 8 hours in air, prepare cobalt acid lithium.
Control resulting cobalt acid lithium size with the sieve of 32 μ m after, prepare Coin-shaped battery shown in Figure 3 in the mode that is similar to example 1.The conservation rate of the detection discharge capacity first time and 100 discharge capacities, it is low to moderate 141mAh/g and 77% respectively.
Can find out from above-mentioned example and comparative example, the cobalt acid lithium that utilizes method of the present invention to obtain has high compacted density, cobalt acid lithium comprises Feret particle size range 0.4-10 μ m and average grain diameter 5 μ m or littler small crystals and the mixture that is positioned at the spherical or oval spherical second particle of 4-30 mu m range that is arranged in perspective view, second particle forms by many above-mentioned small crystalss gatherings, therefore, battery can be filled by a large amount of positive electrode active materials.This means the raising of filling characteristic, because the second particle of closely filling with former particle is spherical or oval spherical.
Use this cobalt acid lithium can improve the conservation rate of discharge capacity and capacity as positive electrode active materials.This reason is that former particle is relatively little, improves the surface area that contacts with electrolyte, and this causes cell reaction easily, improves discharge capacity.In addition, active material is difficult to meticulous pulverizing, even recharge and discharge improve the conservation rate of discharge capacity.
Can find out from above-mentioned example 2, also satisfactory with the correlation of discharge current density.Think that reason is that former particle is relatively little according to lithium cobalt of the present invention, improved and electrolytical contact surface area that this makes cell reaction take place easily.In addition, owing to mutually combining by sintering to the former particle of small part, the resistance between the former particle descends, and this also is one of major reason.
In addition, because particle is in conjunction with firmly, second particle is broken hardly in the preparation electrode, guarantees that electrolyte infiltrates in the slit, and, former particle coming off from the collector body can not taken place.
On the other hand, can find out that tube is singly worn into granular cobalt acid lithium and failed fully to electrically contact, and makes cell performance degradation in former particle from comparative example.In addition, cause the slit filling of former particle or the defective that comes off from collector body a little less than the mechanical strength.
Industrial applicability
As mentioned above, positive electrode active materials of rechargeable nonaqueous electrolytic battery of the present invention and preparation method thereof can improve the discharge capacity of secondary cell, conservation rate and the efficient discharge capacity of discharge capacity, thereby, can prepare good non-aqueous secondary batteries.

Claims (16)

1. positive electrode active materials that is used for rechargeable nonaqueous electrolytic battery is characterized in that being used for the positive electrode active materials of rechargeable nonaqueous electrolytic battery, wherein uses molecular formula LiCoO 2The cobalt acid lithium of expression, described cobalt acid lithium comprises the former particle of small crystals and the second particle that the gathering of a certain amount of small crystals forms, the Feret diameter range that SEM observes the small crystals in the perspective view is 0.4-10 μ m, its average grain diameter is 5 μ m or littler, the scope of second particle is 4-30 μ m, in addition, the mol ratio of Co and Li is 0.97 or bigger and 1.03 or littler.
2. according to the described active material of claim 1, it is characterized in that constituting mutually combining by sintering to the small part small crystals of second particle.
3. according to claim 1 or 2 described active materials, it is characterized in that described second particle is for spherical or oval spherical.
4. according to each described active material of claim 1-3, it is characterized in that second particle account for above-mentioned SEM observe Feret particle diameter 9 μ m in the perspective view or bigger particle 90% or bigger.
5. according to each described active material of claim 1-4, it is characterized in that volume ratio that above-mentioned SEM observes Feret particle diameter 6 μ m in the perspective view or bigger particle account for total mixture 70% or bigger.
6. method for preparing the positive electrode active materials that is used for rechargeable nonaqueous electrolytic battery is characterized in that preparing the method for the positive electrode active materials that is used for rechargeable nonaqueous electrolytic battery, wherein uses molecular formula LiCoO 2The cobalt acid lithium of expression, above-mentioned cobalt acid lithium comprises the former particle of small crystals and assembles the second particle that many above-mentioned small crystalss form, the Feret diameter range that SEM observes the small crystals in the perspective view is 0.4-10 μ m, its average grain diameter is 5 μ m or littler, the scope of second particle is 4-30 μ m, wherein the mol ratio of Co and Li is 0.97 or bigger and 1.03 or littler, method is to mix serving as raw-material cobalt source and lithium salts, this mixture of heat treatment and preparing, wherein the hydroxy cobalt oxide in cobalt source (CoOOH) comprises the second particle of scope 4-30 μ m, and this second particle is formed by the many former particle aggregation of 0.2-0.8 μ m.
7. in accordance with the method for claim 6, it is characterized in that the second particle of above-mentioned positive electrode active materials is for spherical or oval spherical.
8. according to claim 6 or 7 described methods, it is characterized in that constituting the mutually combining by sintering to the small part small crystals of second particle of above-mentioned positive electrode active materials.
9. according to each described method among the claim 6-8, the second particle that it is characterized in that above-mentioned hydroxy cobalt oxide is for spherical or oval spherical.
10. according to each described method among the claim 6-9, it is characterized in that SEM that second particle accounts for above-mentioned positive electrode active materials observe Feret particle diameter 9 μ m in the perspective view or bigger particle 90% or bigger.
11. according to each described method among the claim 6-10, the volume ratio that the SEM that it is characterized in that above-mentioned positive electrode active materials observes Feret particle diameter 6 μ m in the perspective view or bigger particle account for total mixture 70% or bigger.
12., it is characterized in that in oxidizing atmosphere, under 800 ℃-1000 ℃ mixture being heat-treated 4-12 hour according to each described method among the claim 6-11.
13. according to each described method among the claim 6-12, it is characterized in that the cobalt source is a cobaltosic oxide, wherein hydroxy cobalt oxide is as raw material, this cobalt source prepares by 350 ℃ of-800 ℃ of following heat treatment hydroxy cobalt oxides in oxidizing atmosphere.
14. in accordance with the method for claim 13, it is characterized in that cobaltosic oxide is used as above-mentioned cobalt source, cobaltosic oxide comprises second particle, the second particle scope is 4-30 μ m, is arranged in the many former particle that above-mentioned SEM observes the Feret particle size range 0.05-0.8 μ m of perspective view by gathering and forms.
15. according to claim 13 or 14 described methods, the second particle that it is characterized in that above-mentioned cobaltosic oxide is spherical or oval spherical.
16. a rechargeable nonaqueous electrolytic battery is characterized in that serving as component as each described positive electrode active materials among the claim 1-5.
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